JP3015949B2 - Method for producing optically isotropic pitch having high softening point - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an optically isotropic pitch having a high softening point. More specifically, the present invention relates to petroleum-based medium oil / heavy oil, coal-based coal tar /
Can be used as a carbon source for materials such as coal tar pitch and aromatic organic compounds as precursors for general-purpose carbon fibers, activated carbon fibers, carbon-carbon composites, and carbon materials for non-aqueous electrolyte secondary battery negative electrode active materials And a method for producing a high softening point optically isotropic pitch.

[0002]

2. Description of the Related Art A high softening point optically isotropic pitch is used for general-purpose carbon fiber, activated carbon fiber, carbon-carbon composite, non-aqueous electrolyte 2
When using the high softening point optically isotropic pitch as a precursor in a material used for a precursor of a high-performance carbon material such as a carbon material for a secondary battery negative electrode, when producing the carbon material, the carbonization yield And the resulting carbon material has good mechanical or electrical properties.

Produced from petroleum medium / heavy oil, aromatic hydrocarbon simple substance (for example, naphthalene, methylnaphthalene or anthracene), coal-based residue (for example, coal tar or coal tar pitch), etc. Using a high softening point pitch of 150 ° C or more softening point as a precursor of general-purpose carbon fiber, activated carbon fiber, carbon-carbon composite, carbon material for non-aqueous electrolyte secondary battery negative electrode active material,
In order to produce carbon fiber and carbonaceous particles, a method has been used in which radiation and particle production are performed, followed by high-temperature heat treatment to obtain a carbonaceous final product. Fibers and particles that are melted when subjected to a high-temperature heat treatment are directly melted and the form is destroyed. Therefore, in general, the form cannot be maintained during carbonization unless infusibilizing treatment such as oxidation is indispensable. The infusibilization treatment involves treating fibers and particles produced in pitch in an oxidizing gas atmosphere (eg, air, carbon dioxide or carbon monoxide) or an oxidizing liquid atmosphere (eg, aqueous nitric acid or hydrochloric acid) for a long time. In most cases, oxidation heat treatment is performed for one minute to several tens of days while maintaining a temperature of 100 to 350 ° C. in an air atmosphere in consideration of economical and environmental aspects. Consists of Generally 150 ° C softening point
Fibers and particles manufactured using the following pitch as a precursor must be subjected to a long-term heat treatment in such infusibilizing treatment, so that energy consumption is severe and the carbonization yield during carbonization decreases. However, there is a problem that the mechanical properties of the obtained carbon material are lowered and, of course, the production cost is increased.

Therefore, many methods for producing a high softening point optically isotropic pitch have been proposed, and such an existing method will be described as follows. A method of removing low-molecular-weight components from coal-based coal tar or coal-tar pitch by vacuum distillation or solvent extraction, a method of polymerizing low-molecular-weight components in a carbon source by simple thermal polymerization to convert them to high-molecular-weight components, In parallel, two methods have been used to produce optically isotropic pitches having a specific, relatively narrow range of molecular weight distribution from raw materials having a very broad molecular weight distribution. However, there are disadvantages in that the yield is low, and components that easily become mesophase remain upon heating, and there are many problems in pitch uniformity and stability.

[0005] The use of 1,4-benzoquinone as a cross-linking agent in coal tar pitch makes use of Diels-Elder.
There has been a method for producing an optically isotropic pitch by inducing an s-Alder) reaction, but the pitch yield is low,
There is a problem that the oxygen-containing functional group of 4-benzoquinone is already introduced into the pitch to have resistance to oxidation, and it is not economical to use a large amount of 1,4-benzoquinone as a crosslinking agent. There was a disadvantage.

[0006] In the method of adding nitric acid to coal tar and coal tar pitch and performing heat treatment, the reaction is not uniform by reacting a hydrophobic pitch with a water-soluble acid. The disadvantage is that the reaction product is easily solidified due to confusion, or it is difficult to obtain a high softening point optically isotropic pitch that can be homogeneously dissolved or melted in a solvent and heat because the generated pitch is uneven. is there. Recently, it has been known that a method for obtaining mesophase pitch from an aromatic organic compound in a high yield at a relatively low temperature with hydrogen fluoride / boron trifluoride or the like as a catalyst has been developed and commercialized. However, there is a problem that a step of manufacturing a high softening point optically isotropic pitch is not performed.

[0007] A method of increasing the softening point by adding a nitro compound to a petroleum-based intermediate oil or a coal-based residue and subjecting it to a heat treatment is to increase the production cost by adding an expensive nitro compound and to react the nitro compound with a starting material. At this time, there is a problem that the obtained pitch becomes non-uniform due to difficulty in uniformly dispersing the nitro compound. In particular, 1 to 10% by weight of a nitro compound is added to a petroleum medium oil and the temperature is 150 to 400 ° C.
For 1 to 120 minutes to obtain a reformed product, and dissolve the reformed product in a simplex aromatic hydrocarbon solvent to remove the insolubilized precipitate, and recover the solvent with a solution obtained. The production method including obtaining a soluble component by heating and subjecting the soluble component to heat treatment has a problem in that the yield is low, the production process is complicated, and enormous equipment is required. In addition, the method of heat-treating the catalyst by adding aluminum chloride has a problem in that after the reaction is completed, the removal of aluminum chloride used for the catalyst from the obtained pitch is confusing. When carbonaceous material is produced by carbonization, aluminum chloride and the like remaining in the pitch may act as impurities, thereby deteriorating the mechanical properties of the finally obtained carbonaceous material. are doing.

[0008] In order to produce a carbon fiber as a highly functional carbon material, a pitch-based activated carbon fiber, and a carbon material for a negative electrode active material of a non-aqueous electrolyte secondary battery, a precursor having a high softening point optical isotropy is required. The pitch is required to be uniform and uniform in the process of melting or dissolving in heat or a solvent, and furthermore, since a high-purity precursor pitch is required, its softening point, pyridine-soluble component,
Controlling factors such as quinoline solubles arbitrarily, and using a distillate or an aromatic hydrocarbon single substance that does not contain impurities such as metals, high yield and high softening point optically isotropic pitch Researches on the production of high-softening-pitch from a complex mixture such as coal-based residue and petroleum-based medium oil have been conventionally conducted. Excessive thermal decomposition and condensation reactions are likely to occur during the melting stage, such as the production of carbon materials with a reduced pitch, and as a result, gas and insoluble substances are generated, making it impossible to produce the specified carbon material, or a carbon material having extremely poor physical properties. The problem of having to obtain materials frequently occurred.

Accordingly, by adjusting control factors such as softening point, pyridine soluble matter and quinoline soluble matter, a high softening point optically isotropic pitch suitable for infusibilization by oxidation or the like in the melting step of the precursor pitch. There was a need to develop new methods of manufacturing.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to adjust the controlling factors such as the softening point, pyridine solubles and quinoline solubles to adapt the precursor pitch to infusibilization by oxidation at the application stage. An object of the present invention is to provide a method for producing a high softening point optically isotropic pitch. Another object of the present invention is applicable to general aromatic hydrocarbons in general, and particularly coal tar as coal residue, coal tar pitch as coal tar refining residue, petroleum medium / heavy oil and It is an object of the present invention to provide a method for producing a high softening point optically isotropic pitch using a distillate or an aromatic hydrocarbon single substance as a starting material.

[0011]

According to one embodiment of the present invention, a method for producing a high softening point optically isotropic pitch for achieving the above object is provided by a petroleum medium / heavy oil such as naphthalene. An additive such as a halogen molecule is added to a carbon source such as a single substance of an aromatic hydrocarbon such as methylnaphthalene or anthracene, or a coal-based residue such as coal tar or coal tar pitch. An additive treatment step of reacting at 70 to 230 ° C. in addition to 1.2 to 112 parts by weight based on 100 parts by weight of the carbon source;
A reaction step of heating the reaction product obtained in the additive treatment step to 230 to 360 ° C. and further reacting for 1 to 30 hours; and contacting with an inert gas under normal pressure or reduced pressure to obtain a low molecular weight product. A post-processing step for removing hard components.

The carbon source may be C10 + oil content of petroleum medium oil or methylnaphthalene, or may be a carbon source from which free carbon has been removed, and preferably has an aromatic index of 0.18 to 0. .95 hydrocarbons.

In the additive treatment step, the additive is chlorine (C
l ₂ ), thionyl chloride (SOCl ₂ ), sulfuryl chloride (SO ₂ Cl ₂ ), bromine (Br ₂ ), thionyl bromide (S
OBr ₂ ), iodine (I ₂ ), phosphoryl chloride (POC
l ₃₎ or those that have been selected in the group consisting of a mixture of two or more among these may be used.

The post-treatment may be performed at a temperature at which the reaction is completed.

A method for producing a high softening point optically isotropic pitch according to another embodiment of the present invention is a method for producing an aromatic carbon such as a petroleum medium oil / heavy oil such as naphthalene, methylnaphthalene or anthracene. Adding a halogen molecule to a carbon source such as a simple substance of hydrogen, or coal-based residue such as coal tar or coal tar pitch, for example,
The mixed reaction mixture is heated and reacted while being irradiated with ultraviolet rays.

High softening point light according to another embodiment of the present invention
The production method of the isotropic pitch is petroleum medium oil / heavy
Oils, such as naphthalene, methylnaphthalene or en
A single substance of an aromatic hydrocarbon such as thracene, or
For example, coal tar or coal tar pitch
Halogen for carbon source such as coal-based residuemolecule
And a catalyzing step of adding a radical initiator; and mixing
Heating and reacting the reacted reaction mixture.
Wherein the carbon source is 60 to 180 in the catalyzing step.
C. can be heated.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to specific embodiments. In the present invention, coal-based coal tar and coal tar pitch can be used after extracting the included free carbon (fixed carbon) by a solvent or heat filtration, and the intermediate oil as a petroleum-based raw material is not refined. Can be used for

In the additive treatment step, the additive is chlorine (Cl
₂ ), thionyl chloride (SOCl ₂ ), sulfuryl chloride (SO ₂ Cl ₂ ), bromine (Br ₂ ), thionyl bromide (S
OBr ₂ ), iodine (I ₂ ), phosphoryl chloride (POC
l ₃ ) or those selected from the group consisting of mixtures of two or more thereof.

On the other hand, the temperature at which the additive is added to the carbon source,
The addition amount and the heat treatment conditions function as important regulators because they affect the properties or yield of the desired optically isotropic pitch. When the temperature of addition of the additives, particularly the halogen molecules , is less than 70 ° C., there may be a problem that the efficiency of polymerization is reduced.
There may be a problem that the polymerization reaction is rather deteriorated due to rapid boiling of the molecule .

If the amount of the additive is less than 1.2 parts by weight based on 100 parts by weight of the carbon source, promotion of polycondensation by heat treatment is insufficient, and there is no effect of improving the softening point of the obtained pitch. If the amount exceeds 112 parts by weight with respect to 100 parts by weight of the carbon source, a large amount of the additive may remain in the obtained pitch, thereby deteriorating the physical properties of the pitch.

On the other hand, after the addition of the additive,
C. or less than 1 hour, the reaction may not proceed sufficiently. If the heat treatment temperature exceeds 360.degree. C. or the treatment time exceeds 30 hours, severe polymerization may occur. May occur, causing the pitch obtained by the carbon source to become optically anisotropic or coke.

The post-treatment step may be performed at a temperature at which the reaction step is completed, and may be removed by vacuum distillation, steam distillation, or contact with an inert gas at normal pressure and reduced pressure. Such post-treatment steps can also be performed at temperatures below 360 ° C., at which again no anisotropic spheres are formed.

A method for producing a high softening point optically isotropic pitch according to another embodiment of the present invention is a method for producing an aromatic carbon such as a petroleum medium oil / heavy oil such as naphthalene, methylnaphthalene or anthracene. A halogen molecule is added to a carbon source such as a simple substance of hydrogen or coal-based residue such as coal tar or coal tar pitch, for example,
The mixed reaction mixture is heated and reacted while being irradiated with ultraviolet rays.

The present invention relates to a method for inducing polycondensation by adding a halogen molecule to a heat treatment to induce polycondensation, and irradiating the reaction mixture during the reaction with ultraviolet rays to accelerate the radical reaction (Rapid Radical Ind.).
It is characterized by providing a method for easily obtaining a high softening point optically isotropic pitch in a short time by increasing the radical reaction rate between a halogen molecule and a carbon source by applying the method.

As the carbon source, a wide range of organic compounds such as C10 + oil of petroleum medium oil, carbon source from which methylnaphthalene or free carbon has been removed can be used as the carbon source. Can be C10 + oil or methyl naphthalene of high quality oil, which is mostly volatilized and has a very low yield as pitch compared to the conventional production technology. In the present invention, such a highly volatile hydrocarbon is used. The present invention is also characterized in that it can be easily produced with a high softening point and an optically isotropic pitch in a high yield by using the carbon source by halogen treatment and ultraviolet irradiation according to the present invention.

The additives include chlorine (Cl ₂ ), thionyl chloride (SOCl ₂ ), sulfuryl chloride (SO ₂ Cl
₂ ), bromine (Br ₂ ), thionyl bromide (SOBr ₂ ),
A member selected from the group consisting of iodine (I ₂ ), phosphoryl chloride (POCl ₃ ) or a mixture of two or more thereof may be used, which is merely exemplary and It can be easily understood by those having ordinary skill in the art that other suitable halogen molecules may be used.

The additive is used in an amount of 1.2 to 112 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the carbon source.
It may be mixed to the quantity of parts, when the additive is used in less than 1.2 parts by weight, to the catalytic effect of the addition of additives there may be problems become weak, if it exceeds 112 parts by weight However, there may be a problem that the quinoline insoluble content increases.

The reaction mixture can be heated at a temperature in the range of 50 to 180 ° C., preferably 60 to 120 ° C., for 0.5 to 2 hours, preferably 0.8 to 1 hour. If the reaction temperature is very low below 0 ° C., or if the reaction time is less than 0.5 hour, sufficient polycondensation reaction may not be performed, so that the pitch yield may be reduced. If the temperature exceeds 180 ° C or becomes very long, on the contrary, excessive polycondensation occurs, and the quinoline-insoluble content increases, resulting in severe evaporation of low-reactive substances. Can be a problem.

The above-mentioned irradiation of ultraviolet rays can be performed by irradiation with ordinary ultraviolet rays or the like. Such ultraviolet rays can be obtained by purchasing ordinary ultraviolet rays or the like supplied to those having ordinary knowledge in the technical field. It is self-evident that it is understood to be known enough to be used.

[0030] The reaction is allowed to warm to complete the product to 230 to 360 ° C. for 2 to 12 hours further the reaction of Seraru, if heated in less than 2 30 ° C. problems unreacted If the temperature exceeds 360 ° C., there may be a problem that the pitch becomes optically anisotropic or coke due to excessive polymerization.

A method for producing a high softening point optically isotropic pitch according to still another embodiment of the present invention is a method for producing a petroleum medium / heavy oil, for example, an aromatic compound such as naphthalene, methylnaphthalene or anthracene. A catalyzing step of adding a halogen molecule and a radical initiator to a carbon source such as a hydrocarbon single substance or a coal-based residue such as coal tar or coal tar pitch; and heating the mixed reaction mixture; A carbon source may be heated to 60 to 180 ° C. in the catalyzing step.

The present invention is characterized in that a radical initiator is further added during the reaction between a carbon source and a halogen molecule to increase the reaction rate and reduce the reaction time for conversion to pitch.

The carbon source may be a C10 + oil component of petroleum medium oil or a carbon source from which methyl naphthalene or free carbon has been removed. Most of these carbon sources are volatilized by conventional production techniques, and are used as pitch. According to the present invention, a hydrocarbon having a very low yield, such as a highly volatile hydrocarbon, is easily treated with a halogen source and a radical initiator using the carbon source in a high yield and a high softening point. The feature is that it can be manufactured in pitch.
In particular, the C10 + oil content of petroleum-based medium oil is determined by thermogravimetric analysis (TG
A: Thermal Gravity Analysis
s) Result The substance is mostly volatilized at 200 ° C. The results of elemental analysis are 89.05% of carbon, 8.90% of hydrogen, 1.9% of nitrogen
3%, sulfur 0.12%, and aromatization degree (fa) is 5
It is a material that is 1.4%, 30% yield compared with the conventional manufacturing technology
It is known that it is impossible to manufacture as a pitch below.

The additives include chlorine (Cl ₂ ), thionyl chloride (SOCl ₂ ), sulfuryl chloride (SO ₂ Cl
₂ ), bromine (Br ₂ ), thionyl bromide (SOBr ₂ ),
A member selected from the group consisting of iodine (I ₂ ), phosphoryl chloride (POCl ₃ ) or a mixture of two or more thereof may be used.

The additive is used in an amount of 1.2 to 112 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the carbon source.
It can be mixed in parts by weight.

[0036] In addition to the additive in the present invention, and further comprising a radical initiator as a catalyst, the additive
If the agent is used in less than 1.2 part by weight, to the catalytic effect of the addition of additives there may be problems become weak, 11
If it exceeds 2 parts by weight, there may be a problem that the quinoline insoluble content increases.

The radical initiator is benzoyl peroxide, dibutyl hydroperoxide (di-t-dibutyl hydro).
roperoxide, acetyl peroxide (Acety)
organic peroxide (Orga) such as lperoxide)
nick Peroxide) and a, a'-azobisisobutyronitrile (AIBN; a, a'-Azobis)
isobutyronitrile), a, a'-azobismethylisobutyrate (a, a'-Azobism)
An azo compound such as ethyl isobutylate, or a member selected from the group consisting of a mixture of two or more thereof may be used, and these radical initiators are also merely exemplified. It will be readily apparent to one of ordinary skill in the art that other suitable radical initiators may be used.

The radical initiator is the additive 100
1 to 20 parts by weight, preferably 5 to 1 part by weight
5 parts by weight may be used, and when the radical initiator is mixed with less than 1 part by weight of the additive, there may be a problem that the effect of mixing the radical initiator is very small, and conversely, If the amount exceeds 20 parts by weight, problems such as side reactions may occur.

In the catalyzing step, heating may be performed within a temperature range of 50 to 180 ° C., preferably 60 to 120 ° C., or for 0.5 to 2 hours, preferably 0.8 to 1 hour. .

When the heating temperature is lower than 50 ° C., there is a problem that the reaction is not easily initiated. On the contrary, when the heating temperature is higher than 180 ° C., rapid decomposition and volatilization of the radical initiator occur. Therefore, there may be a problem that the effect of adding the radical initiator is reduced.

In the catalyzing step, after the radical initiator is added, the additive may be added,
It adds a radical initiator to an already heated carbon source
It is based on experimentally revealed that the catalyst effect can be made more uniform by adding an agent .

In the reaction step, the reaction mixture is reacted at a temperature of 60 to 180 ° C. for 0.5 to 2 hours, and then heated and further heated at a temperature of 230 to 360 ° C. for 2 to 12 hours. .

The heating at 230 to 360 ° C. for 2 to 12 hours is understood as a subsequent step in the process of decomposing the halogen molecules and the radical initiator which can remain in the pitch as a reaction product after the reaction. Can be
Also, when the heating is performed at less than 230 ° C., there is a problem that the reaction is unreacted. When the heating is performed at more than 360 ° C., there is a problem that excessive polymerization causes the pitch to become optically anisotropic or coke.

Hereinafter, preferred examples and comparative examples of the present invention will be described. The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention.

Example 1 Coal tar was converted to tetrahydrofuran (Tetrahyd).
(rofuran) was added to 30 parts by weight based on 100 parts by weight, stirred, filtered, and the filtrate was evaporated and concentrated to purify. While stirring 100 parts by weight of the purified coal tar at 120 ° C., 13 parts by weight of bromine (Br ₂ ) was added dropwise as an additive over 1 hour, and the mixture was further stirred at that temperature for 1 hour, and the resulting mixture was placed in a nitrogen atmosphere. After heating to 320 ° C and heating and stirring for 7 hours 30 minutes,
The unreacted low molecular components are removed by contacting with nitrogen gas under reduced pressure of 100 mmHg for 5 minutes to obtain the desired high softening point optically isotropic pitch. The resulting pitch is shown in Table 1 below. It was shown to. The carbonization yield was measured by the fixed carbon content determination method of JIS K2425.

Example 2 100 parts by weight of coal tar purified in the same manner as in Example 1 were stirred at 120 ° C. while adding bromine (Br) as an additive.
₂ ) After instilling 6.5 parts by weight over 1 hour,
The mixture obtained by further stirring at that temperature for 1 hour was heated to 320 ° C. in a nitrogen atmosphere, heated and stirred for 15 hours, and then brought into contact with nitrogen gas at 350 ° C. for 45 minutes under a reduced pressure of 10 mmHg. The desired high softening point optically isotropic pitch was obtained by removing the low molecular components of the reaction, and the resulting pitch was as shown in Table 1 below.

Example 3 100 parts by weight of coal tar purified by the method of Example 1 were stirred at 120 ° C. while adding bromine (Br) as an additive.
₂ ) After instilling 3.3 parts by weight over 1 hour,
The mixture obtained by further stirring at that temperature for 1 hour was heated to 320 ° C. in a nitrogen atmosphere, heated and stirred for 25 hours, and then brought into contact with nitrogen gas at 350 ° C. for 45 minutes under a reduced pressure of 10 mmHg. The desired high softening point optically isotropic pitch was obtained by removing unreacted low molecules, and the composition of the obtained pitch is shown in Table 1 below.

Example 4 Chlorine gas was added as an additive at a rate of 0.1 l / min (5 parts by weight) for 30 minutes while stirring 100 parts by weight of coal tar purified by the method of Example 1 at 150 ° C. After the mixture was poured into coal tar, the mixture was further stirred at that temperature for 1 hour, heated to 300 ° C. in a nitrogen atmosphere, heated and stirred for 20 hours, and then stirred at 350 ° C. for 45 minutes.
An unreacted low molecular component is removed by contacting with nitrogen gas under a reduced pressure of 0 mmHg to obtain a desired high softening point optically isotropic pitch. The resulting pitch is shown in Table 1 below. Indicated.

Example 5 15 parts by weight of pulverized coal tar pitch powder was added to 100 parts by weight of tetrahydrofuran, stirred, filtered, and the filtrate was evaporated and concentrated to purify. Refined coal tar pitch 100
While stirring parts by weight at 120 ° C., bromine (B
r ₂ ) After instilling 13 parts by weight over a period of 1 hour,
The mixture obtained by further stirring at that temperature for 1 hour was heated to 320 ° C. in a nitrogen atmosphere, heated and stirred for 9 hours, and then brought into contact with nitrogen gas at 350 ° C. for 45 minutes under reduced pressure of 10 mmHg. The desired high softening point optically isotropic pitch was obtained by removing unreacted low molecular components, and the resulting pitch is shown in Table 1 below.

Example 6 5 parts by weight of thionyl chloride as an additive was dropped into a coal tar for 1 hour while stirring at 120 ° C. 100 parts by weight of coal tar purified in the same manner as in Example 1.
The mixture obtained by further stirring at that temperature for 1 hour was heated to 300 ° C. in a nitrogen atmosphere, heated and stirred for 18 hours, and then brought into contact with nitrogen gas at 350 ° C. for 45 minutes under a reduced pressure of 10 mmHg. The desired high softening point optically isotropic pitch was obtained by removing unreacted low molecular components, and the resulting pitch is shown in Table 1 below.

Example 7 A mixture of 100 parts by weight of coal tar purified in the same manner as in Example 1 and 5 parts by weight of
The mixture obtained by stirring for 2 hours at 300 ° C. was heated to 300 ° C. in a nitrogen atmosphere, heated and stirred for 12 hours, and then stirred for 3 hours.
An unreacted low molecular component is removed by contacting with nitrogen gas under reduced pressure of 10 mmHg at 50 ° C. for 45 minutes to obtain a desired high softening point optically isotropic pitch. The results are shown in Table 1 below.

Example 8 100 parts by weight of coal tar purified as in Example 5 was charged to a 200 W ultraviolet-ray lamp (Ultra-violet).
500 with an immersion lamp
Then, the mixture was heated to 150 ° C. and melted, and then 5 parts by weight of sulfuryl chloride was added. The mixture was reacted at 100 ° C. with irradiation with ultraviolet rays for 2 hours while stirring, and then heated to 250 ° C. For 6 hours, and after completion of the reaction, nitrogen gas is passed for 2 hours to remove unreacted or low-reacted molecules to obtain the desired high softening point optically isotropic pitch. The softening point and yield of the obtained pitch are also shown in Table 1.

Example 9 A 500 ml reactor was charged with 200 parts by weight of C10 + oil as a carbon source, heated to 140 ° C. and melted.
While irradiating ultraviolet rays, 200 parts by weight of bromine is applied for 2 hours.
After the reaction, the reaction was further continued for 10 hours while blowing nitrogen gas to obtain the desired high softening point optically isotropic pitch, and the softening point of the obtained pitch was obtained. And the yields are also shown in Table 1.

Example 10 100 parts by weight of coal tar pitch purified as in Example 5 was charged into a 500 ml reaction tank, heated to 150 ° C., and then 5 parts by weight of sulfuryl chloride and 0.1% of benzoyl peroxide.
After adding 5 parts by weight and reacting with stirring for 2 hours, the temperature was raised and further reacted at 300 ° C. for 6 hours. After the reaction was completed, nitrogen gas was passed for 2 hours and unreacted or low-reacted molecules were reacted. Was removed to obtain a desired high softening point optically isotropic pitch. The softening point and yield of the obtained pitch are also shown in Table 1.

Example 11 200 parts by weight of an oil component of C10 + and 1 part by weight of benzoyl peroxide were placed in a 500 ml reactor and heated to 80 ° C.
The reaction is carried out by dropping 200 parts by weight of bromine over 2 hours. After the reaction, the temperature is raised to 250 ° C. while blowing nitrogen gas and heated for 10 hours to obtain the desired high softening point optically isotropic pitch. The softening point and yield of the obtained pitch are also shown in Table 1.

Comparative Example 1 100 parts by weight of coal tar purified in the same manner as in Example 1 were stirred at 120 ° C. for 2 hours and then at 340 ° C. for 15 hours to remove low molecular components as in Example 1. Thus, the desired optically isotropic pitch was obtained, and the composition of the obtained pitch is shown in Table 1 below.

Comparative Example 2 100 parts by weight of coal tar pitch purified as in Example 5 were stirred at 120 ° C. for 2 hours and then at 340 ° C. for 10 hours to remove low molecular weight components. A high softening point optically isotropic pitch was obtained and the resulting pitch is shown in Table 1 below.

COMPARATIVE EXAMPLE 3 While refluxing C10 + 200 parts by weight, 2
After stirring for 10 hours, the temperature was raised again to 320 ° C. while removing the hard oil under a reduced pressure of 10 mmHg.
After stirring for an hour, the mixture was contacted with nitrogen gas at 350 ° C. for 45 minutes under a reduced pressure of 10 mmHg, but all were volatilized.

[0059]

[Table 1]

[0060]

According to the present invention, a petroleum medium oil having a degree of aromatization of 60% or less, which cannot be produced by the conventional method or can be produced only at a low yield, and Utilizes most of coal-based residues including aromatic hydrocarbon simple substance and petroleum medium / heavy oil, and aromatic hydrocarbons, has high softening point and excellent infusibility, and solid content in molten state Since it is hardly contained, it is possible to obtain a high-yield optically isotropic pitch which is homogeneous, has excellent solvent solubility, and has a relatively low content of ash such as inorganic substances and metal powder.

According to the present invention, not only the softening point of the produced pitch can be adjusted, but also the solubility of the solvent (eg, toluene-soluble, pyridine-soluble and quinoline-soluble) can be arbitrarily adjusted. A method of manufacturing a fine pitch is possible.

The pitch produced in the present invention is a raw material and an intermediate material of a high-performance carbon material such as a general-purpose carbon fiber, an activated carbon fiber, a carbon-carbon composite, and a carbon material for a negative electrode of a non-aqueous electrolyte secondary battery. Can be used.

Although the present invention has been described in detail only with respect to the specific examples described above, it will be apparent to those skilled in the art that various changes and modifications can be made within the technical idea of the present invention. It is natural that such changes and modifications fall within the scope of the appended claims.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Min Hee-hoon, Korea No.103-406, Aooka-nare Apartment, Tamin-dong, Yuseong-gu, Daejeon-gu, Republic of Korea (72) Inventor Kim Rong-euk-yu Tamin, Yuseong-gu, Daejeon, Korea 462-5, Dong Sejong Apartment 109-904 (72) Inventor Yoon Seung-ho, 462-5, Tanmin-dong, Yuseong-gu, Daejeon-gu, Korea Sejong Apartment 104-304 (72) Inventor Lee Da-Hang Incheon, Korea Jinbo apartment 104-4403, Manju 6-dong, Namdong-gu, Seoul (72) Inventor Hiroshi Hayashi 104-203, Banpo-dong, Banpo-dong, Seoul Seocho-gu, Seoul (56) References JP 62-197307 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C10C 3/02 C10C 1/20 C10C 3/04

Claims (6)

(57) [Claims] 1. A petroleum medium / heavy oil, for example a single substance of an aromatic hydrocarbon such as naphthalene, methylnaphthalene or anthracene, or, for example, coal tar or coal tar pitch. An additive treatment step in which an additive such as a halogen molecule is added to a carbon source such as a fresh coal-based residue in an amount of 1.2 to 112 parts by weight based on 100 parts by weight of the carbon source and reacted at 70 to 230 ° C .; Reacting the reaction product obtained in the agent treatment step to 230 to 360 ° C. and further reacting for 1 to 30 hours; and contacting with an inert gas under normal pressure or reduced pressure to obtain a low molecular weight hard component. A method for producing an optically isotropic pitch having a high softening point. Wherein said at additive treatment step, the additive is a salt of thionyl (SOCl _2), sulfuryl chloride (SO ₂ Cl
₂ ), bromine (Br ₂ ), thionyl bromide (SOBr ₂ ),
Iodine (I ₂ ), phosphoryl chloride (POCl ₃ ; Pho
sporusoxychloride) or these
_2. The high softening point optical element according to claim 1, wherein said substance is selected from the group consisting of two or more mixtures of chlorine (Cl ₂ ) and bromine (Br ₂ ). Manufacturing method of isotropic pitch. 3. A petroleum medium / heavy oil, for example a single substance of an aromatic hydrocarbon such as naphthalene, methylnaphthalene or anthracene, or, for example, coal tar or coal tar pitch. Additive treatment in which an additive such as a halogen molecule is added to a carbon source such as a fresh coal-based residue in an amount of 1.2 to 112 parts by weight based on 100 parts by weight of the carbon source, and is reacted with ultraviolet irradiation at 70 to 230 ° C. A reaction step in which the reaction product obtained in the additive treatment step is heated to 230 to 360 ° C. and further reacted for 1 to 30 hours; and a low molecular weight by contacting with an inert gas under normal pressure or reduced pressure. A method for producing an optically isotropic pitch having a high softening point, comprising: Wherein the additive is a salt thionyl by the additive treatment step (SOCl _2), sulfuryl chloride (SO ₂ Cl _2),
Thionyl bromide (SOBr ₂ ), iodine (I ₂ ), phosphoryl chloride (POCl ₃ ; Phosphorus oxy)
chloride or chlorine (Cl ₂ ), odor
Element (Br ₂₎ two or more manufacturing method of the high softening point optically isotropic pitch according to claim 3, characterized in that one selected in the group consisting of a mixture of in plus . 5. A petroleum medium / heavy oil, for example a simple substance of an aromatic hydrocarbon such as naphthalene, methylnaphthalene or anthracene, or, for example, coal tar or coal tar pitch. a coal residue 1 to 20 with respect to the halogen molecule 100 parts by weight of a radical initiator together with 1.2 to 112 parts by weight of additives such as halogen molecules to the carbon source 100 parts by weight of a carbon source such as A reaction step of heating and reacting the mixed reaction mixture; and a post-treatment step of contacting with an inert gas under normal pressure or reduced pressure to remove low-molecular-weight hard components. The carbon source can be heated to 60 to 180 ° C. in the carbon source heating step, and the reaction mixture can be heated to 230 to 360 ° C. in the reaction step. Method of manufacturing a softening point optically isotropic pitch. 6. The radical initiator used in the catalysis step is benzoyl peroxide, di-t-dibutyl hydroperoxide (di-t-Dib).
organic peroxides such as acetyl hydroperoxide and acetyl peroxide, and a,
a'-azobisisobutyronitrile (AIBN; a,
a'-Azobisisobutyronitril
e), azobismethylisobutyrate (a, a'-az
A method for producing an optically isotropic pitch having a high softening point, which is selected from the group consisting of an azo compound such as obismethyl isobutylate, or a mixture of two or more thereof.